Soluble polymers hydrophobic interaction

In aqueous solutions of Cm-(EO)n amphiphilic molecules, two interesting features are observed. First, isotropic micellar solutions undergo phase separation on heating. Such behavior is typical of hydrophobic interaction and is also observed for several water-soluble polymers. Hydrophobic interaction results from a change of order in the water structure [54]. Second, at high concentration, liquid crystalline phase behavior is observed with several structures [55]. 

In the field of water-soluble polymers, hydrophobic interactions are... 

PVP is a nonionic water-soluble polymer that interacts with water-soluble dyes to form water-soluble complexes with less fabric substantivity than the free dye. Additionally, PVP inhibits soil redeposition and is particularly effective with synthetic fibers and synthetic cotton blends. The polymer comprises hydrophilic, dipolar imido groups in conjunction with hydrophobic, apolar methylene and methine groups. The combination of dipolar and amphiphilic character make PVP soluble in water and organic solvents such as alcohols and partially halogenated alkanes, and will complex a variety of polarizable and acidic compounds. PVP is particularly effective with blue dyes and not as effective with acid red dyes. 

In the case of water-soluble polymers, there is another factor that has to be taken into account when considering solubility, namely the possibility of hydrophobic interactions. If we consider a polymer, even one that is soluble in water, we notice that it is made up of two types of chemical species, the polar functional groups and the non-polar backbone. Typically, polymers have an organic backbone that consists of C—C chains with the majority of valence sites on the carbon atoms occupied by hydrogen atoms. In other words, this kind of polymer partially exhibits the nature of a hydrocarbon, and as such resists dissolution in water. 

Hydrophobic interactions of this kind have been assumed to originate because the attempt to dissolve the hydrocarbon component causes the development of cage structures of hydrogen-bonded water molecules around the non-polar solute. This increase in the regularity of the solvent would result in an overall reduction in entropy of the system, and therefore is not favoured. Hydrophobic effects of this kind are significant in solutions of all water-soluble polymers except poly(acrylic acid) and poly(acrylamide), where large heats of solution of the polar groups swamp the effect. 

The hydrophobic interaction results in the existence of a lower critical solution temperature and in the striking result that raising the temperature reduces the solubility, as can be seen in liquid-liquid phase diagrams (see Figure 5.2a). In general, the solution behaviour of water-soluble polymers... 

A class of systems extensively investigated by means of PFG-NMR are colloids. They are usually hydrophobically modified water-soluble polymers, that is, polymers with a water-soluble skeleton bearing one or more hydrophobic units, which allow the self-assembling of the polymer in water solution and the interaction with surfactants.77... 

Random distribution of a significant number of hydrophilic NVIAz units along the polymer chain could result in uniform hydrophilization. This, in turn, could lead to a loss of ability for the coil-globule transition, which is caused by the hydrophobic interactions. As a result, such copolymers should be water-soluble over a wide temperature range. 

Xu QH, Gaylord BS, Wang S, Bazan GC, Moses D, Heeger AJ (2004) Time-resolved energy transfer in DNA sequence detection using water-soluble conjugated polymers the role of electrostatic and hydrophobic interactions. Proc Natl Acad Sci USA 101 11634-11639... 

Very recently a new method was developed that opens the possibility to polymerize even hydrophobic monomers in aqueous solution. This method is based on the finding that hydrophobic monomers can be made water-soluble by incorporation in the cavities of cyclodextrins. It has to be mentioned that no covalent bonds are formed by the interaction of the cyclodextrin host and the water-insoluble guest molecule. Obviously only hydrogen bonds or hydrophobic interactions are responsible for the spontaneous formation and the stability of these host-guest complexes. X-ray diffraction pattern support this hypothesis. Radical polymerization then occurs via these host-guest complexes using water-soluble initiators. Only after a few percent conversion the homogeneous solution becomes turbid and the polymer precipitates. 

There are a number of different enthalpic interactions that can occur between polymer and packing, and in many cases multiple interactions can exist depending on the chemical structure of the polymer. Enthalpic interactions that are related to water-soluble polymers include ion exchange, ion inclusion, ion exclusion, hydrophobic interactions, and hydrogen bonding (12)- Other types of interactions commonly encountered in SEC, as well as in all other chromatographic separations, are dispersion (London) forces, dipole interactions (Keeson and Debye forces), and electron-donor-acceptor interactions (20). 

Hydrophobic interactions seem to have negligible effects on polymer com-plexation, since, in this case, this temperature-dependent solubility change shows a positive temperature dependence in optical T% changes. Therefore, hydrogen bonding forces are probably the primary intermolecular interactions. 

As is being discussed, polymers used to prepare micelles exhibit a LCST that can be deLned as the temperature at which the polymer phase separates (Heskinsand Guillet, 1968). Below the LCST, the polymer/micelle is soluble, but it precipitates at temperatures above the LCST. The diameter of these micelles rapidly rises at temperatures above the LCST, due to hydrophobic interactions that result in the aggregation of the micelles (Kohori et al., 1998). This effect of temperature on size was shown to be reversible, since the micellar architecture was maintained after lowering the temperature below the LCST (Chung et al., 1999). 

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